CN104114766B - For improvement of the system and way of paper and paperboard - Google Patents

For improvement of the system and way of paper and paperboard Download PDF

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Publication number
CN104114766B
CN104114766B CN201280061403.6A CN201280061403A CN104114766B CN 104114766 B CN104114766 B CN 104114766B CN 201280061403 A CN201280061403 A CN 201280061403A CN 104114766 B CN104114766 B CN 104114766B
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paper
anionic
polyacrylamide
charged ion
straight chain
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CN104114766A (en
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汤姆·林德斯特伦
安娜·斯韦德贝里
米卡埃尔·安克福什
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Innventia AB
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic

Abstract

The present invention relates to a kind of method for the preparation of Paper or cardboard, it comprises formation cellulosic suspension, make this suspensoid flocculating, drain to equipment to form paper page by this suspensoid, then this paper page dry, it is characterized in that using the 3-component flocculation system improving and being shaped to make this suspensoid flocculating, this system comprises: a) positively charged ion of the straight chain of following material or ampholyte copolymer: i) acrylamide, with ii) formula (I) material using halogen as counterion; B) at least one water soluble ingredient of anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide it is selected from; And c) inorganic particles, thus this flocculation system not containing dispersible in water or the anionic organic polymer of side chain. The present invention also relates to this flocculation/retention system in the purposes manufactured in Paper or cardboard, and relates to the paper and paperboard thus produced.

Description

For improvement of the system and way of paper and paperboard
Technical field
The present invention relates to a kind of method for the manufacture of Paper or cardboard, comprise and form cellulosic fibre suspensoid, make this suspensoid flocculating, drain to equipment to form paper page by this suspensoid, then this paper page dry, it is characterized in that using the 3-component flocculation system improving and being shaped to make this suspensoid flocculating, this system comprises: a) positively charged ion of the straight chain of following material or ampholyte copolymer: i) acrylamide, with ii) formula I material using halogen as counterion; B) at least one water soluble ingredient of anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide it is selected from; And c) inorganic particles, thus this flocculation system not containing dispersible in water or the anionic organic polymer of side chain. Nanofibrils Mierocrystalline cellulose (NFC) can be added in this flocculation system.
The present invention also relates to flocculation/retention system in the purposes manufactured in Paper or cardboard material, and relates to the paper and paperboard thus produced.
Background technology
During preparing paper and paperboard material, cellulosic fibre raw material is drained on wire-cloth. Wet net is transferred to press section, is then transferred to dryer section, in dryer section, make paper dry and finally in rolling drum (tambour), be collected as paper roll or board rolls. Because present paper industry pays close attention to the consumption reducing starting material and the energy, so adding filler (clay, grinding calcium carbonate or precipitated chalk, titanium dioxide etc.). Modern paper machine runs at high speed, and has big filtration rate in the net portion stage, and this needs to use flocculation agent to keep fines and filler on the net.
It is always almost filler retention and sheet formation to two parameters that good papermaking is most important. Sheet formation (or paper uniformity coefficient) is one of the most important qualitative characteristics of paper material, and high fines/filler retention is important processing parameter. The latter for the product rate of paper machine and wet end (wet-end) stability and z to filler distribution uniformity coefficient very important. By adopting polytype retention system to provide filler to keep, the feature of all these systems is all potent flocculation agent. Flocculation agent deterioration sheet formation, therefore has delicate balance between sheet formation and retention, is referred to herein as and keeps-shaping relation.
Due to the development now (such as, the filler content of higher white-water system degree of closure, higher machine speed, raising and two net are shaped) of modern paper technology, wet end chemistry becomes more complicated. Which results in the demand of the raising to chemistry adjuvant (comprising retention aid (flocculation agent)) performance.
Paper technology use retention aid to keep filler and fines. The common ground of retention aid is that they cause fines and filler material to be gathered into bigger unit, and during dewatering, these unit are kept in wet paper web. High retention is all favourable in many, such as, higher machinery efficiency, to processing condition change compared with fast-response, less recycled material and less material transhipment between paper machine and coupled white-water system. As potent flocculation agent, retention aid deterioration sheet formation is known. The uniformity coefficient of sheet formation also depends on the flocculation of fiber in shaped segment and the interpolation of shearing condition and other chemistry adjuvants. Multiple paper performance is had disadvantageous effect by bad sheet formation, such as, and the intensity of paper, opaqueness and impressionability. It is keep level at the acceptable filler that reaches kept or improve sheet formation simultaneously to the challenge of papermaker now.
Introduce many different retention system in today's marketplace, can divide into groups according to their chemical property, aggregation of multiple or system component number. The mechanism of action deeply describing retention aid in some summaries and development (see such as, " SomeFundamentalChemicalAspectsonPaperForming "T " Fundamentalsofpapermaking " the 1st volume, the 309th page, BakerC, F and PuntonVW write, Mech.Eng.Pub.Ltd. (London) 1989).
Early stage in the 1980s, introduce first microparticle system, and these systems occupy market now. Particulate base retention aid is usually based on the combination of cationic polymers and anionic inorganic colloid.
The particulate base retention aid of two kinds of initial business covers unsticking soil in conjunction with anionic colloidal silica and based on cationic polyacrylamide in conjunction with negatively charged ion based on cationic starch. After these precursors, promote the exploitation of new particulate base retention system. During nineteen nineties, report some new particulate base retention system, comprise novel microparticle system and the transformation of existing system.
Now, keeping/dewatering system field is still in the exploitation carrying out continuing. More the retention system of recent development is usually multicomponent system. But, also there is the progress about novel particulate, such as, the particulate that the what is called being made up of organic granular is crosslinked.
Major part business retention aid now can reach acceptable filler and keep level, though also like this in two net forming mills at a high speed. This part ground is interpreted as the throw out that the shearing resistance that they can produce can heavily to flocculate after distribution is cut. This heavy flocculation occurs after the suspensoid processed by microparticle retention aid disperses. The principal benefits of microparticle retention aid is that they are on the useful impact of dehydration. Reversible research for flocculation also demonstrates this kind of benefit of microparticle system. But, it should not allow this retention aid to produce the throw out with too high throw out intensity, because this will impair sheet formation.
Only there is the balance that several systematic researchs can be used for describing filler and keep between sheet formation, and whether some retention aid of research is more harmful to sheet formation than other further. But, the something in common of these available research is difficult to break the mutual dependence kept and between sheet formation or fiber dispersion.
Nearest research is also it has proven convenient that for both traditional retention system and modem particulate system, all be difficult to break the mutual dependence between keeping and being shaped. But, have statement in the claim of patent documentation to be combined side chain/crosslinked polyelectrolyte with particulate and will be conducive to keeping/sheet formation relation (WO98/29604, CA2425197). Also have the three compositions system proposed containing binary microparticle system and organic fine particles will be conducive to this object (US6,524,439). But, acrylamide and N had not both been mentioned in this patent application, N, N-trimethylamino-ethyl propylene acid esters, N, N, the cationic copolymer of N-trimethylammonium-2-amino-ethyl Methacrylamide or 3-acrylamide-3-methyl-butyl-trimethyl-ammonium chloride, does not mention nanofibrils cellulose materials yet.
Paper machine headbox (headbox) is usually equipped with " turbulent flow generator ". Turbulent flow generator is basically tube bank (tubebank), accelerates raw material and broken fiber throw out in this tube bank. The basic function of turbulent flow generator is that transverse direction (CD) material of fiber is evenly distributed, and obtains fiber uniform CD material distribution in paper. When leaving the tube bank in head box through the fiber of dispersion, they start flocculation in the turbulent flow of decay. This is exposed to by during dispersion fiber and tends to make the viscous of this fiber bending and the fact of dynamic force to explain. When turbulent flow decays, fiber tends to recapture its original shape. If there being many fibers in unit volume, so they can not freely stretch out. On the contrary, they will stop at strain location (strainedposition), and interlock by normal force and frictional force, form fibre network (throw out). Turbulent flow is more high, and the tendency heavily flocculated is more strong.
Another important discovery is, the anionic polyacrylamide adding high molecular can be decayed turbulent flow, and the additive improved sheet formation as one-component. Shortcoming be dehydration be subject to serious impact, cause such system almost do not have practicality (Lee, P. andT. (1989) Nord, PulpPaperRes.J., 4 (2), 61-70 page). Such as, system that complexity is higher (in the present patent application those disclosed) must be utilized to relax the disadvantageous effect of impaired dehydration.
Invention general introduction
Unexpectedly, having found that following flocculation system can significantly improve and do not sacrificed dehydration at the sheet formation of the level of keeping specified, this flocculation system is combined with following material: a) positively charged ion of the straight chain of following material or ampholyte copolymer: i) acrylamide and ii) the formula I material of halide mode; And at least one water soluble ingredient b) being selected from anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide; And c) inorganic particles, thus, said composition not containing dispersible in water or the anionic organic polymer of side chain. The most important thing is, it has been found that with such three compositions system can avoid to row water mitigation, and therefore not taking at the filtration rate in net portion as cost provides the sheet formation of improvement.
Therefore, the present invention relates to the purposes of flocculation system, and relate to a kind of method for the preparation of Paper or cardboard, the method comprises formation cellulosic suspension, makes this suspensoid flocculating, drains to device to form paper page by this suspensoid, then this paper page dry, it is characterised in that make this suspensoid flocculating with the use of this flocculation system. The present invention also relates to the paper and paperboard adopting the method and system to produce.
Without being bound by any theory, it is believed that this flocculation system mechanism behind is relevant with the turbulent flow decay during being shaped.
By adding NFC in three components flocculation system, under the existence of fiber, soluble high-molecular amount polyelectrolyte and NFC, the synergistic effect of decay turbulent flow can be obtained, and because this enhancing sheet formation. The interpolation of NFC also by the combination that improves between fiber and in the feed combination between other compositions strengthen paper intensity.
Detailed Description Of The Invention
The present invention relates to a kind of method for the manufacture of Paper or cardboard, comprise formation cellulosic suspension, make this suspensoid flocculating, drain to equipment to form paper page by this suspensoid, then this paper page dry, it is characterized in that using flocculation system to make this suspensoid flocculating, this flocculation system comprises:
A) positively charged ion of the straight chain of following material or ampholyte copolymer:
I) acrylamide, and
Ii) formula I material using halogen as counterion
Wherein:
R1It is H or CH3,
X is O or NH,
R2It is C1-C4Alkyl, it is replaced by cationic;
B) at least one water soluble ingredient of anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide it is selected from; With
C) inorganic particles,
Thus, described flocculation system not containing dispersible in water or the anionic organic polymer of side chain.
According to an embodiment, this flocculation system also contains the Mierocrystalline cellulose (NFC of nanofibrils; Also the Mierocrystalline cellulose being often called microfibrillated, MFC).
This suspensoid is the water suspension of paper pulp (pulp) fiber. According to an embodiment, filler and/or pigment can be added. This suspensoid can be pulp suspension, the fibre pulp being especially made up of hardwood fiber and/or cork fibrous. According to an embodiment, this paper pulp is refining hardwood and/or softwood bleached Kraft pulp. The cellulosic fibre that can use in the present invention can be bleaching, half bleaching or unbleached sulfite pulp, vitriol (ox-hide) paper pulp or soda pulps; Bleaching, half bleaching or unbleached (chemistry) mechanical pulp, (chemistry) thermomechanical pulp, and these paper pulp are with the mixture of any mixture ratio. Initial paper pulp and both fibers of drying and recirculation can be used according to the present invention, and the filamentary material from the vegetable fibre of broad variety, cork fibrous and hardwood fiber. Therefore, can use non-wood such as cotton, mestha, multiple grass, and regeneration cellulosic fibre.
The pH value of pulp suspension can be 6 to 9, such as, and 8.0. NaHCO can be added3As the catalyzer carrying out applying glue with alkyl ketene dimer.
Many cationic polymerss are to hydrolysis-susceptible, and can easily become both sexes, therefore incorporate such straight-chain polymer in present inventive concept. The high-molecular weight polymer of positively charged ion or both sexes is suitably positively charged ion and/or amphiprotic polyacrylamide, it is preferable that cation acrylamide based polyalcohol. The cationic degree (the cationic monomer mole % in polymer backbone) of this polymkeric substance can be 1 mole of % to 100 mole of %, suitably 1 mole of % to 80 mole of %, and preferred 1 mole of % to 60 mole of %. According to an embodiment, molecular weight is higher than 2 �� 106Dalton, such as, higher than 4 �� 106, higher than 5 �� 106, higher than 10 �� 106, higher than 20 �� 106, higher than 30 �� 106, higher than 40 �� 106, higher than 50 �� 106, higher than 60 �� 106, higher than 70 �� 106, higher than 80 �� 106, higher than 90 �� 106. Molecular weight also can at any interval range obtained by arbitrary above-mentioned molecular weight, such as, 2 �� 106Dalton to 20 �� 106Dalton, such as, 4 �� 106Dalton to 15 �� 106Dalton. The upper limit is unimportant.
Positively charged ion or Amphiphatic high polymer amount straight-chain polymer can be the multipolymer of acrylamide with the formula I material using halogen as counterion. According to an embodiment, formula I material is selected from N, N, N-trimethylammonium-2-amino-ethyl acrylate, N, N, N-trimethylammonium-2-amino-ethyl Methacrylamide or 3-acrylamide-3-methyl-butyl-trimethyl-ammonium chloride.
The electric charge of anionic polyacrylamide is unimportant, but should be chosen as and make this Polymer adsorption minimumization, with dispersing material in the feed. According to an embodiment, molecular weight is higher than 2 �� 106Dalton, such as, higher than 4 �� 106, higher than 5 �� 106, higher than 10 �� 106, higher than 20 �� 106, higher than 30 �� 106, higher than 40 �� 106, higher than 50 �� 106, higher than 60 �� 106, higher than 70 �� 106, higher than 80 �� 106, or higher than 90 �� 106. Molecular weight also can at any interval range obtained by arbitrary above-mentioned molecular weight, such as, 2 �� 106Dalton to 20 �� 106Dalton, such as, 4 �� 106Dalton to 15 �� 106Dalton. The upper limit is unimportant.
This anionic polyacrylamide is straight chain. Non-ionic polyacrylamide may also be straight chain. Polyethylene oxide may also be straight chain. According to the present invention, it has been found that, the polyethylene oxide of the anionic polyacrylamide of straight chain, the non-ionic polyacrylamide of straight chain and straight chain is better shaped than crosslinked polymkeric substance. But, slight crosslinked polymkeric substance also can obtain acceptable result. Therefore, according to the present invention, nonionic and polyacrylamide and polyethylene oxide respectively can containing based on completely crosslinked polymkeric substance at the most 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% crosslinked, or any interval obtained by arbitrary above-mentioned per-cent.
According to an embodiment, anionic polymer is the water-soluble polyacrylamide derivative of the high molecular weight of straight chain, and such as, anionic copolymer is such as the Percol156 of BASF.
Anionic polymer is prepared by hydro-polyacrylamide polymkeric substance etc., such as, prepare by making such monomer and (methyl) vinylformic acid and salt, 2-acrylamido-2-methyl propane sulfonic acid salt, sulfoethyl-(methyl) acrylate, vinyl sulfonic acid, styrene sulfonic acid, toxilic acid or other diprotic acid or their salt or its polymerization of mixtures those.
Anion degree according to the poly-propionic acid amide of an embodiment, the negatively charged ion of anionic polymer amount and/or nonionic is the anionic group of 0 mole of % to 100 mole of %, suitably lower than 80 moles of %, and is preferably 0% to 60%.
The molecular weight of polyacrylamide or polyethylene oxide can be higher than 106Dalton. The upper limit is unimportant. Molecular weight is more high, and the efficiency of this polymkeric substance decay turbulent flow is more high.
According to an embodiment, molecular weight is higher than 2 �� 106Dalton, such as, higher than 4 �� 106, higher than 5 �� 106, higher than 10 �� 106, higher than 20 �� 106, higher than 30 �� 106, higher than 40 �� 106, higher than 50 �� 106, higher than 60 �� 106, higher than 70 �� 106, higher than 80 �� 106, or higher than 90 �� 106. Molecular weight also can at any interval range obtained by arbitrary above-mentioned molecular weight, such as, 2 �� 106Dalton to 20 �� 106Dalton, such as, 4 �� 106Dalton to 15 �� 106Dalton.
The pitch-based sphere of this negatively charged ion and/or non-ionic polymers is that 50g/ ton Paper or cardboard is to 2000g/ ton Paper or cardboard, it is preferable that 100g/ ton Paper or cardboard is to 1500g/ ton Paper or cardboard.
Inorganic particles can be selected from silica-based particles, silicon-dioxide microgel, colloid silica, silicon dioxide gel, silica dioxide gel, polysilicate/ester, cationic silicon dioxide, aluminosilicate, polysialates, borosilicate, poly-borosilicate, zeolite, wilkinite, hectorite, smectite, montmorillonite, nontronite, saponite, sauconite, fiber rod stone (hormites), attapulgite, sepiolite and other swellable clays. Such as, according to an embodiment, this inorganic particles can be selected from siliceous material, such as, is selected from and covers unsticking soil and colloid silica, such as anionic silica and Na montmorillonite (HydrocolSH).
Can add the nanofibrils cellulose (NFC) in flocculation system is that a kind of cellulose fibril material by the nano-scale with the high-aspect-ratio ratio of width (length with) forms. Typically being of a size of width 5 nanometers to 20 nanometers, length is many to 2000 nanometers. NFC shows (viscosity) character of retrogradation at the standard conditions, but when shaking, stir or when being otherwise in stressed condition (stressedstate), can flow along with the time (become rare, low viscosity). Being separated protofibril originating from arbitrary cellulose, described cellulose origin comprises plant and wood-based fibre (wood pulp cellulose), such as, is changed by high pressure and high speed impact equal. High energy efficiency is produced usually to be needed to carry out some enzymes/chemical/mechanical pre-treatment before equal one changes. Except dry strong (drystrength) adjuvant effect of NFC in paper-making process, according to the present invention, NFC is also for the turbulent flow that decays in paper-making process.
The amount that nanofibrils Mierocrystalline cellulose can add is that the ton number 1kg/ ton based on Paper or cardboard is to 80kg/ ton, it is preferable that 2kg/ ton is to 40kg/ ton.
The electric density of anionic polyacrylamide used is unimportant, but should be chosen as and make absorption minimumization to this polymkeric substance, with by dispersion of materials in raw material.
According to the present invention, the component of flocculation system can be introduced respectively.
Preferably, first by the positively charged ion of straight chain or Amphiphatic high polymer amount polyelectrolyte introducing system, then, inorganic particles, such as anionic polyacrylamide and NFC optionally and is wherein added. The order of addition of chemical additive below is unimportant.
Cellulosic suspension can contain filler. Filler can be made up of the arbitrary general filler material used. Such as, such as, filler can be made up of clay (kaolin), grinding calcium carbonate or precipitated chalk, talcum (talk) or titanium dioxide. Exemplary filler material also comprises the polymer packing of synthesis.
Confirm, the flocculation system according to the present invention of the positively charged ion or ampholyte copolymer, anionic polyacrylamide and/or non-ionic polyacrylamide and/or polyethylene oxide and inorganic particles that comprise straight chain is decayed turbulent flow in paper-making process, and improves sheet formation. If flocculation system is also containing NFC, then situation is especially true.
The present invention also relates to such flocculation system and keeps for improving in the technique preparing Paper or cardboard, dewaters and the purposes of sheet formation, and this flocculation system comprises positively charged ion or the ampholyte copolymer of a) straight chain of following material: i) acrylamide and ii) the formula I material of halide mode; B) negatively charged ion and/or non-ionic polyacrylamide and/or polyethylene oxide; And c) inorganic particles.
Mentioned above add that necessary amendment is applied to the purposes of the product (that is, paper and paperboard) of this flocculation system and this technique about all details of component and technology characteristics. This is applicable to the feature of the exemplary molecular weight, linear degree (linearity), ion degree (ionicity), inorganic particles and the NFC that use.
All publications mentioned by herein are all incorporated to herein with what law allowed to greatest extent as quoted passage. Now, by by non-limiting example hereafter, the present invention is described.
Accompanying drawing explanation
The present invention is set forth by the following drawings.
Fig. 1 illustrates that total one-tenth paper number (totalformationnumber) (0.4mm to 30mm) of the three kinds of cationic polyacrylamides (polymer A is to C) do not waited for molecular weight at machine direction is as the function of filler retention (%). Polymkeric substance used in test of keeping in this single-component system is three kinds of commercially available cationic polyacrylamides: polymer A (Mw=3 �� 106Dalton to 4 �� 106Dalton, electric density=+ 0.82 milligramequivalent/g); Polymer B (Mw=6 �� 106Dalton to 8 �� 106Dalton, electric density=+ 1.02 milligramequivalent/g); Polymkeric substance C (Mw=10 �� 106Dalton to 11 �� 106Dalton, electric density=+ 1.06 milligramequivalent/g).
Polymkeric substance pitch-based sphere is that 500g/ ton is to 1500g/ ton. This research carries out in the R-F machine (R-F-machine) for meticulous paper material (hardwood/softwood is than 9/1), adds grinding calcium carbonate (GCC) filler (based on solids content) of 20%.
Fig. 2 illustrates, for two kinds of binary composition retention system: polymer B (600g/ ton is to 1800g/ ton) and colloid silica (3kg/ ton); Polymer B (300g/ ton is to 900g/ ton) and Na-cover unsticking soil (2kg/ ton), keep the function of (%) as GCC filler total one-tenth paper number (0.4mm to 30mm) of machine direction. This research for meticulous paper material (hardwood/softwood is than 9/1) R-F machine (see " APilotWebFormertoStudyRetention-FormationRelationships ", Svedberg, A. andT.NordicPulpandPaperResearchJournal, 25 (2) (2010) 185-194) in carry out, add 20% filler (GCC) (based on solids content).
Fig. 3 illustrates feed system (dosagesystem) (arrow above flowline) and measurement point (arrow below flowline) in the feedstream of R-F machine. Size is not proportional.
Fig. 4 illustrates that total one-tenth paper number (0.4mm to 30.0mm) at machine direction (MD) is as the function of the amount (g/t) of the anionic polymer added. The data of (crosslinked, partial cross-linked with straight chain) anionic polymer that three kinds of structures are different are shown, study described three kinds of anionic polymers in conjunction with C-PAM (cationic polyacrylamide) and negatively charged ion sodium illiteracy unsticking soil. This research carries out in the R-F machine (R-F-machine) for meticulous paper material (hardwood/softwood is than 9/1), and the precipitated chalk (PCC) of interpolation 25% is as filler (based on solids content). It is constant (being respectively 400g/t and 2000g/t) that C-PAM and sodium cover the interpolation of unsticking soil. The residence time of C-PAM is 5.6s, and anionic polymer is 2.3s, and to cover unsticking soil be 2.0s.
Fig. 5 illustrates that total one-tenth paper number (0.4mm to 30.0mm) at machine direction (MD) is as the function of filler retention (%). Show the data of the three compositions system (reference hierarchy adds anionic polymer) of binary reference hierarchy (C-PAM (400g/ ton) and illiteracy unsticking soil (2kg/ ton)) and different anions polymkeric substance. This anionic polymer different according to structure (crosslinked, partial cross-linked with straight chain) and this anionic polymer be added to 200g/ ton to 1200g/ ton not etc. This research carries out in the R-F machine (R-F-machine) for meticulous paper material (hardwood/softwood is than 9/1), adds 25% filler (PCC) (based on solids content).
Fig. 6 illustrates with 103(10^3) cartographic represenation of area of pixel dehydration (see " ImprovementoftheRetention-FormationRelationshipusingThre ee-componenentretentionaidsystems ", Svedberg, A. andT.NordicPulp&PaperResearchJournal (2012), 27 (1), 86-92) as the function of amount (g/ ton) of the anionic polymer added. Show the data of the three compositions system (C-PAM+ anionic polymer+sodium covers unsticking soil) with different anionic polymers. This anionic polymer different according to structure (crosslinked, partial cross-linked with straight chain). This research carries out in the R-F machine for meticulous paper material (hardwood/softwood is than 9/1), adds 25% filler (PCC) (based on solids content). The interpolation of C-PAM and illiteracy unsticking soil is constant (being respectively 400g/t and 2000g/t).
Fig. 7 illustrates with 103(10^3) dehydration of the cartographic represenation of area of pixel with always become paper number (0.4mm to 30.0mm) as the function of drying line (dryline) position at machine direction (MD). Drying line is moved in three ways: carry out lower shifting by improving vacuum tightness from reference state; By shifting on the overdose of anionic polymer; And by reducing, paper tinsel number and vacuum are moved. This research carries out in the R-F machine for meticulous paper material (hardwood/softwood is than 9/1), adds 25% filler (PCC) (based on solids content).
Embodiment
Embodiment 1 test of commercially available retention system
The present embodiment illustrates, for 5 kinds of extensive different commercially available retention system, the relation kept between sheet formation is unique. First three system is the cationic polyacrylamide (C-PAM) with different molecular weight, and the 4th kind of system is containing the second-component system (Compozil) with the C-PAM of colloidal silica sol combination. 5th kind of system is that another kind covers the second-component system of de-colloidal sol (Hydrocol) containing C-PAM and sodium. All systems are all extensively in paper industry.
R-F (keep-be shaped) machine used is designed in net portion that research is kept, the fourdrinier wire forming mill of the pilot scale of sheet formation and drainage rates. Svedberg before, and Lindstrom A., T. at " APilotWebFormertoStudyRetention-FormationRelationships " NordicPulpandPaperResearchJournal, 25 (2) (2010) 185-194 have described the details of R-F machine. Use the paper machine of fourdrinier wire type, and ran under 260m/ minute. Stock consistency is 5g/l, and paper page gram is heavily 60g/m2��
Being defined by following formula by retention (Rf) in the first of per-cent filler:
Rf = ( 1 - C 2 C 1 ) * 100 - - - [ 1 ]
Wherein, C1It is the packing density in head box, and C2It it is the packing density in net hole (wirepit).
Sheet formation is determined by the FUJI method of Sweden MoReResearch. FUJI method is measured at gram localized variation in double recipe face (" Themeasurementofmassdistributioninpapersheetsusingabetar adiographicmethod " according to �� radiography, Norman, B and Wahren, D.Sv.Papperstid, 77 (11), 397 (1974); Beta-radiationbasedongrammageformationmeasurement-Radiog rammethodsapplicabletopaperandlightweightboard, Norman, B, (2009), NordicStandardizationProgrammeReportNo.5).
The result obtained from the method shows as into paper number. Become paper number be to the local in paper gram heavily change measure. Therefore, high number represent poor sheet formation and deterioration about intensity, printability and paper performance attractive in appearance.
Paper pulp used is refining hardwood and the kraft pulp of cork bleaching. Batching is hardwood (HW) (mainly the birch 90% to 96%) of 90% and the mixture of the cork (SW) (China fir of about 45% to 60%, all the other are pine) of 10%. Filler used is grinding calcium carbonate slurry (GCC). The filler content of paper is about 20%.
Polymkeric substance used in test of keeping in single-component system is three kinds of commercially available cationic polyacrylamides: polymer A (Mw=3 �� 106Dalton to 4 �� 106Dalton, electric density=+ 0.82 milligramequivalent/g); Polymer B (Mw=6 �� 106Dalton to 8 �� 106Dalton, electric density=+ 1.02 milligramequivalent/g); Polymkeric substance C (Mw=10 �� 106Dalton to 11 �� 106Dalton, electric density=+ 1.06 milligramequivalent/g).
In binary composition system, the silicon-dioxide (SilicaNP, EkaChemicals) of polymer B and colloid or sodium cover unsticking soil (HydrocolSH, CibaSpecialtyChemicals) combination.
For the cationic polyacrylamide (polymer A is to C) that three kinds of molecular weight do not wait, determine the total one-tenth paper number at machine direction as filler retention (%) function, and result in FIG illustrates, for these three kinds of C-PAM, show the single relation unrelated with its Mw between sheet formation keeping. Be shaped deterioration filler retention raising simultaneously, and this is the result of expection, because the flocculation improved causes the shaping kept and deteriorate improved.
In the 2nd group of experiment, the retention aid system of research binary system type. First it is the polymer B combined with silicon dioxide gel (Compozil) and the polymer B combined with sodium illiteracy unsticking soil (Hydrocol). Result figure 2 illustrates. Equally, the relation kept/be shaped follows single-relation. When the result of the result of Fig. 1 and Fig. 2 is compared, however, be evident that nearly all have single relation for all five kinds of systems.
In a word, embodiment 1 illustrates, for many commercially available retention system, the relation kept/be shaped is almost identical.
Embodiment 2: according to the present invention, keeps/shaping relation by adding anionic polymer improvement
In the present embodiment, carry out multiple experiment, wherein in binary polymer system, with the addition of the third component, and study on keeping/the impact of sheet formation relation.
Use Pilot Paper Machine in the same manner as in Example 1 and identical paper pulp (hardwood/softwood=9/1). Under the level of filler of 20%, it may also be useful to PCC (precipitated chalk) substitutes GCC. Use machine speed in the same manner as in Example 1 and denseness.
The all polymkeric substance retention aids used all are provided by BASF. According to supplier, give the character of all components in Table 1. Using the acrylamide and the N that are called C-PAM, N, N-trimethylamino-ethyl propylene acid esters is as cationic flocculant (Percol178). The commercial goods of all the other components is called: linear anionic polymkeric substance (Percol156), partial cross-linked anionic polymer (M305), crosslinked anionic polymer (M200) and sodium cover unsticking soil (HydrocolSH).
The character of the retention aid that table 1 uses
System component Electric density1 Intrinsic viscosity2 Normal viscosity3
C-PAM + 1.15 milligramequivalents/g 11dl/g -
Linear anionic polymkeric substance -1.76 milligramequivalents/g 14dl/g -
Partial cross-linked negatively charged ion -2.16 milligramequivalents/g 10dl/g -
Crosslinked negatively charged ion -2.50 milligramequivalents/g - 2mPa.s
Illiteracy unsticking soil -0.34 milligramequivalent/g - 30mPa.s
1Use MutekTMParticle charge detector (PCD) is measured.
Titration reagent used is (i) diallyl dimethyl ammoniumchloride (0.001N) for anionic polymer; And (ii) is for the potassium polyvinyl sulfate (0.001N) of cationic polymers. The approximate molecular weight of these two kinds of titration reagent is 2 �� 105Dalton. Methods analyst according to PAP-SOP01-19 covers unsticking soil.
2Suspended level viscometer is used to determine in 1M sodium-chlor buffered soln the specific viscosity of test component at various concentrations. Depict the specific viscosity of reduction relative to concentration, and obtain intrinsic viscosity by being extrapolated to infinite dilution degree. Polymer chain is more long, and intrinsic viscosity (dl/g) is more high. Testing method is with reference to jsACSMOTNo:7.
3The value of given illiteracy unsticking soil is the direct body viscosity (bulkviscosity) of 5% solution. Using BrookfieidLVT viscometer to characterize the normal viscosity of anionic polymer (0.1% solution), the method is called that L.A. tests method 20.
Retention aid component in this three compositions system is C-PAM, different A-PAM (straight chain, partial cross-linked and crosslinked), and last na montmorillonite. First add C-PAM (0.4kg/ ton), then add anionic polymer (0.2kg/ ton is to 1.2kg/ ton), finally add na montmorillonite (2kg/ ton). The order of addition of latter two additive is unimportant.
Under the machine speed of 260m/ minute, it may also be useful to the velocity rate being injected into net (jet-to-wire) of 1:2, production gram is heavily 60g/m2Containing have an appointment 20% the paper of filler. Stock consistency is 5g/l, and the volumetric flow rate of head box is 910l/ minute. Following table 2 summarizes the experiment condition (dosage and residence time) of the retention system evaluated. Fig. 3 shows the feed system in the feedstream of R-F machine.
The experiment condition of table 2. in pilot scale weber is tested.
System component Dosage (kg/ ton) Residence time * (s)
C-PAM 0.4 5.6
Linear anionic polymkeric substance 0.2-1.2 2.3
Partial cross-linked 0.2-1.2 2.3
Anionic polymer 0.2-1.2 2.3
Polynite 2.0 2.0
* the residence time is corresponding to from the time being added into head box.
Evaluate retention such as embodiment 1 and become paper value.
The present embodiment illustrates how anionic polyacrylamide improves as extra additive and keeps/shaping relation and draining characteristics. This three compositions system anionic polymer and negatively charged ion based on cationic polyacrylamide (C-PAM), high molecular in the way of hereafter described covers unsticking soil. This high molecular weight anionic polymer is different according to dosage and structure. Table 1 gives the characteristic of polymkeric substance.
Show all retention system of evaluation in table 3.
The retention system that table 3. uses in this work
Program Cationic flocculant Anionic polymer Particulate
1 C-PAM - Polynite
2 C-PAM Straight chain A-PAM Polynite
3 C-PAM Partial cross-linked Polynite
4 C-PAM Crosslinked A-PAM Polynite
High molecular weight anionic polymer is on the impact kept and be shaped
Object is that research high molecular weight anionic polymer is on the impact kept and be shaped. Add the anionic polymer studied, and be combined containing the binary microparticle system of 0.4kg/ ton cationic polyacrylamide (C-PAM) and 2.0kg/ ton negatively charged ion illiteracy unsticking soil. Fig. 4 to 6 shows the impact of the anionic polymer of increasing amount and the importance of anionic polymer structure.
Fig. 4 illustrates that the total one-tenth paper number at machine direction is as the function of the amount (g/ ton) of the anionic polymer added. This result demonstrates the different trend depending on the anionic polymer structure used. When use straight chain with partial cross-linked polymkeric substance time, and the increase along with the amount added, significantly improves shaping. Best sheet formation is obtained at the highest Study Polymer Melts dosage (1200g/ ton) place. On the other hand, for crosslinked polymkeric substance, it is shaped and does not still rely on dose of polymer equally.
The retention of filler is still in identical level (about 50%), unrelated with the amount of the polymkeric substance of the negatively charged ion added and structure. This forming results reported in Fig. 4 is combined, and obtains relation in Figure 5, illustrates the shaping of the function as filler retention (%). In Figure 5, the data of (that be cross-linked, partial cross-linked with straight chain) both three compositions systems of binary reference hierarchy (C-PAM and cover unsticking soil) and different anionic polymer structures are shown. Keep-sheet formation relation do not change substantially, unrelated with the interpolation of C-PAM and polynite in this second-component system.
Result display in Fig. 5 can destroy the dependency kept be shaped, that is, can improve and be shaped and do not impair and keep. This improvement, by adding extra anionic polymer, obtains in conjunction with C-PAM and illiteracy unsticking soil. This effective with partial cross-linked anionic polymer for straight chain, but invalid for crosslinked polymkeric substance. The display of binary reference hierarchy is kept and be there is linear relationship between being shaped, and that wherein improves keeps the shaping with deterioration. Along Trendline, the amount independent of the anionic polymer (in three compositions system) added of cationic polymers (in second-component system) increases. As shown in Figure 5, the amount of the anionic polymer added is more high, is shaped more good. The interesting feature adding A-PAM improves simultaneously and keeps and be shaped. Crosslinked polymkeric substance slightly improves to be kept, but does not improve shaping. Important conclusion is, polymkeric substance and the partial cross-linked polymkeric substance of straight chain are effective equally.
An independent experiment is repeated the trend reported in Fig. 4 and Fig. 5. Show the circulation ratio of the first and second height tested wherein using partial cross-linked polymkeric substance in the diagram.
Embodiment 3: according to the present invention, adds anionic polymer to de-water mitigation
Different from the favourable impact of sheet formation, the extra anionic polymer that adds causes drainage rates to reduce.
Add A-PAM by the dehydration slowed down in paper machine be known (Lee, P. andT. (1989) Nord.PulpPaperRes.J., 4 (2), 61-70 page). Therefore, disclosed paper machine checks dehydration in testing in example 2.
Dehydration is quantized according to the vertical deviation of the drying line on the network segment. The method used is based on scattering of light, and uses charge coupled device (CCD) photographic camera, with the change along with dehydration, drying line is carried out imaging. The boundary line that drying line is considered as between scattering region and non-scatter region (that is, region) before dried region and drying line. The variable quantity of dehydration is turned to the area of adjacent wet structure by a series of images treatment step. Providing result is 10 with standard deviation3(10^3) area of pixel, wherein high numeral is relevant with bad dehydration (see " ImprovementoftheRetention-FormationRelationshipusingThre ee-componenentretentionaidsystems ", Svedberg, A. andT.NordicPulp&PaperResearchJournal (2012), 27 (1), 86-92).
Figure 6 illustrates this result, wherein for 3 three compositions systems, will with 103(10^3) dehydration of the cartographic represenation of area of pixel provides as the function of the amount (gram/ton) of the anionic polymer added.
Result in Fig. 6 is clearly. When the amount with partial cross-linked anionic polymer of the straight chain added increases, dehydration number significantly increases. High dehydration number is relevant with bad draining. When using crosslinked polymkeric substance, do not observe de-water mitigation.
From these arguments can inference, if to be utilized the advantage of the shaping of improvement, it should combine the system with good water separation capability to use this system. When relating to improvement dehydration, microparticle system has special advantage, Compozil (cationic polyacrylamide/cationic starch combination silica colloidal sol) that described microparticle system is such as combined with na montmorillonite and Hydrocol (cationic polyacrylamide/cationic starch starch).
Embodiment 4: according to the present invention, adds anionic polymer to shaping and de-water mitigation
Because dehydration is subject to adding the impact of the amount of high anionic polymer, whether the improvement that research is shaped is caused (see Fig. 7) by the de-water mitigation of the chemical process changed or change.
Fig. 7 illustrates with 103(10^3) dehydration of the cartographic represenation of area of pixel with always become paper number as the function of drying line (dryline) position at machine direction (MD). Drying line is moved in three ways: carry out lower shifting by improving vacuum tightness from reference state; By shifting on the overdose of anionic polymer; And by reducing, paper tinsel number and vacuum are moved.
The experimental design that result be figure 7 illustrates is change drying line in online position from reference to position in the way of machinery and chemistry. Arrange for the machine of binary reference hierarchy (C-PAM (400g/ ton) and illiteracy unsticking soil (2kg/ ton)) and standard and obtain with reference to position. Mechanically by reducing paper tinsel number and vacuum, and by adding extra anionic polymer in the way of chemistry, the position of drying line is all changed identical top record position (upperregister) by the two. Anionic polymer is partial cross-linked, and adds with maximum dose level (1200g/ ton), in conjunction with C-PAM (400g/ ton) and illiteracy unsticking soil (2kg/ ton). Move under also making drying line by raising vacuum. This experiment carries out in the R-F machine for meticulous paper material (hardwood/softwood is than 9/1), adds 25% filler (PCC) (based on solids content).
Fig. 7 illustrates with 103(10^3) dehydration of the cartographic represenation of area of pixel with always become paper number as the function of drying line (dryline) position at machine direction (MD). Dehydration number is more high, and the position of drying line is more high. Can reaching a conclusion from Fig. 7, the improvement of shaping shown in figures 2 and 4 is that the chemical mechanism produced due to the overdose of anionic polymer is caused. When mechanically the position of drying line being changed into relative to reference to position being moved and during lower shifting, sheet formation is not affected.
Embodiment 5: according to the present invention, the decay of turbulent flow
The present embodiment illustrates how the combination of different fibers, anionic polyacrylamide and NFC decays turbulent flow. By research when by pulp suspension pump to pipe time the pressure drop of this suspensoid and under the existence of cellulosic fibre, anionic polyacrylamide A-PAM and NFC, measure pressure drop set up this experiment. When pumps water, pressure drop is P0, and when pumping contains the fiber suspension of multiple added ingredients, pressure drop is P1. Then drag reduction (DR) is defined as=(P0-P1)/P0��
Drag reduction is more high, and the attenuation degree of turbulent flow is more high.
Table 4 shows in multiple fluid with the drag reduction (%) of two kinds of flows.
As shown in table 4, cellulosic fibre, A-PAM and MFC/NFC have drag reduction effect. If there is both fiber and A-PAM, so there is the additive effect greatly strengthened by adding MFC/NFC. Should for the mixing of flow optimization A-PAM and MFC/NFC of raw material.

Claims (18)

1. the method for the preparation of Paper or cardboard, comprise: form cellulosic fibre suspensoid, make described suspensoid flocculating, drain to equipment to form paper page by described suspensoid, then dry described paper page, it is characterized in that using the 3-component flocculation system improving and being shaped to make described suspensoid flocculating, described system comprises:
A) positively charged ion of the straight chain of following material or ampholyte copolymer:
I) acrylamide, and
Ii) formula I material using halogen as counterion
Wherein:
R1It is H or CH3,
X is O or NH,
R2It is C1-C4Alkyl, it is replaced by cationic;
B) at least one water soluble ingredient being selected from anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide, wherein said anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide are straight chains; And
C) inorganic particles,
Thus, described flocculation system not containing dispersible in water or the anionic organic polymer of side chain.
2. method according to claim 1, wherein said formula I material is selected from N, N, N-trimethylammonium-2-amino-ethyl acrylate, N, N, N-trimethylammonium-2-amino-ethyl Methacrylamide or 3-acrylamide-3-methyl-butyl-trimethyl-ammonium chloride.
3. method according to any one of claim 1 and 2, the positively charged ion of wherein said straight chain or the molecular weight of ampholyte copolymer are higher than 106Dalton.
4. method according to claim 3, the positively charged ion of wherein said straight chain or the molecular weight of ampholyte copolymer are higher than 2 �� 106Dalton.
5. method according to claim 3, the positively charged ion of wherein said straight chain or the molecular weight of ampholyte copolymer are higher than 4 �� 106Dalton.
6. method according to any one of claim 1 to 5, the positively charged ion of wherein said straight chain or the cationic degree of ampholyte copolymer are 1 mole of % to 100 mole of %.
7. method according to claim 6, the positively charged ion of wherein said straight chain or the cationic degree of ampholyte copolymer are 1 mole of % to 60 mole of %.
8. method according to any one of claim 1 to 7, the molecular weight of wherein said negatively charged ion and/or non-ionic polyacrylamide is higher than 106Dalton.
9. method according to claim 8, the molecular weight of wherein said negatively charged ion and/or non-ionic polyacrylamide is higher than 2 �� 106Dalton.
10. method according to any one of claim 1 to 9, the ion degree of wherein said negatively charged ion and/or non-ionic polyacrylamide is the anionic group of 0 mole of % to 100 mole of %.
11. methods according to claim 10, the ion degree of wherein said negatively charged ion and/or non-ionic polyacrylamide is 0 mole of % to 60 mole of %.
12. methods according to any one of claim 1 to 11, wherein inorganic particles is selected from siliceous material.
13. methods according to claim 12, wherein said inorganic particles is selected from and covers unsticking soil and colloid silica.
14. methods according to claim 12, wherein said inorganic particles is selected from anionic silica and Na polynite.
15. methods according to any one of claim 1 to 14, wherein said flocculation system also comprises microfibril Mierocrystalline cellulose and/or nanofibrils Mierocrystalline cellulose.
16. flocculation systems are used in for the preparation of the technique of Paper or cardboard to improve the purposes kept, dewater and be shaped, and described flocculation system comprises:
A) positively charged ion of the straight chain of following material or ampholyte copolymer:
I) acrylamide,
Ii) formula I material using halogen as counterion
Wherein:
R1It is H or CH3,
X is O or NH,
R2It is C1-C4Alkyl, it is replaced by cationic;
B) at least one water soluble ingredient being selected from anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide, wherein said anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide are straight chains; And
C) inorganic particles,
Thus, described flocculation system not containing dispersible in water or the anionic organic polymer of side chain.
17. Paper or cardboards, it comprises:
A) positively charged ion of the straight chain of following material or ampholyte copolymer:
I) acrylamide,
Ii) formula I material using halogen as counterion
Wherein:
R1It is H or CH3,
X is O or NH,
R2It is C1-C4Alkyl, it is replaced by cationic;
B) at least one water soluble ingredient being selected from anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide, wherein said anionic polyacrylamide, non-ionic polyacrylamide and polyethylene oxide are straight chains; And
C) inorganic particles,
Thus, described Paper or cardboard not containing dispersible in water or the anionic organic polymer of side chain.
18. paper and paperboard according to claim 17, it is also containing nanofibrils Mierocrystalline cellulose.
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